Direct dye planographic printing compositions



-a number of disadvantages. it is not possible to produce designs withex- Patented July 30, 1946 DIRECT DYE PLAN OGRAPHIC PRINTINGCOMPOSITIONS Chester A. Amick,Bound Brook, N. :Lassignor to AmericanCyanamid Company, Bound Brook, N. 3., a corporation of Maine No Drawing.Application December 23, 1944, Serial No. 569,624

20 Claims. .1

This invention relates to putty compositions suitable for planograpliicprinting on cellulosic material and leather employing dyes which arecapable of being directlyaflixed to cellulosic material withoutmordanting,

.In the past the printing of cellulosic material has been accomplishedalmost exclusively by use of the intaglio method. In this method .arelatively free flowing printing paste containing the color to beprinted is applied to an engraved printing roll, usually copper, forexample by means of a furnisher roller, the excess .paste scraped offthe roller so that paste remains only in the depressions, and the rollerapplied to the fabric in a printing machine. This procedure, whilesatisfactory for many types of designs, In the first place,

'tremely fine, close fitting, interwoven, multicolored lines without acertain amount of running or smudging of the lines, because it isnecessary to have a rather free flowing printing paste or otherwise itwill not print satisfactorily.

Mul'ti-colorprinting is also a very serious prob lem because each colorrequires a separate roll and a sharp print requires accurate alignmentand synchronism of the different printing rolls. When a-great numberjofcolors are to be printed a further disadvantage is the large amount ofcapital which has to be tied up in engraved rollers. v

'Planographic printing in which the surface is contacted with a solidputty or block of color and a portion of the color is transferred toform a print presents many operating advantages. This method of printinghas not been applied to cellulosic fibers because when it was attemptedto prepare direct dye compositions in the form of putties they showed ashort softening range and in many cases were friable. The resultingprints showed specks and other unevenness and were not satisfactory.When it is attempted to use large vamounts of glycerin or similarhygroscopic agents theproduct is still not satisfactory and does notkeep in humid atmospheres which makes it impossible to use in commercialprinting plants.

According to the present invention i have found that when putties areprepared containing dyes capable of being directly afiixed to cellulosicmaterial without mordanting, using the customary carbohydrate gum suchas dextrin, produots "having a long softening range can be obtained ifthere is present an amide 'of carbonic,

thiocarbonic or cyanuric 'acids. The common amides are urea, thioureaand melamine, and in the case of urea and thiourea at least the amide isalso an excellent fixing agent, thus performing both functions. Whileurea and thicurea are fixing agents, they :arein no sense mordants, thatis to say, theydo not react with the dyestufi toiform insoluble lakes.It is not desired to limit the present invention to ;a particular theoryof action, but it seems reasonably certain that there is some chemical:reaction "or zoom-bination between the amide and carbohydrate. In thecase of urea and 'thiourea, products having many of the properties ofthermoplastic synt-he'ti-c resins are obtained, 'the urea or thi'oureaappearing "to react with the dextrin. In the case of melamine this resinformation is not apparent, although there -may well'be some reactionbecause melaminedoes not enhance the printing character'istics of theputty "and increases the softening range of the putty,

The various 'amides'are not-all equally effective. Urea is the best.Thiourea gives almost as good results as urea but melamine, whilepermitting the production of useful prints, is not as effective'aseither urea or thiourea.

While thepresence of'the amideis the principal featured the presentinvention and permits the production of useful printing 'putties withdirect colors, .Jfor best results I fin'd that certain otherconstituents .are desirable, although not essentia'lrfor obtainingusable prints. 'Thus, lfind that the incorporationin the putty of a waxymaterial, particularly a glyceryl monoes'ter of a higher fatty acid,controls the plasticity of the putty, aids in giving the -maximumsoftening range and also appears to enhance the transfer of the color inplanographic printing, and in a more specific aspect of the inventionthe-presence of such a waxy material is included.

Another featurefadvantageous in producing prints of maximum quality, isthe incorporation in the ,putty of a soap such as a low titre oliveoil-soap. The soap appears to improve the sharpness and strength of theprint, but is not as important a;feature as the incorporation of thewaxy material.

While the present invention is useful with a wide variety ofcarbohydrate gums best results are obtained when the gums are morehighly dextrinized than is common practice in ordinary printing pastes.Usually in such cases natural gums or a rather heavy bodied, notextensively dextrinized carbohydrate is employed, such as a to expectthat these materials would also give better bodied putties forplanographic printing. I have found, however, that the contrary is. thecase when'dealing with putties containing direct dyes suitable forplanographic printing, the best putties being obtained when highlydextrinized materials such as yellow corn dextrin are used. Thisconstitutes a feature ofthe preferred embodiment of the'presentinvention and is of importance where results of the highest quality arerequired, although entirelysatisfactory prints can be obtained with lesshighly dextrinized materials.

It is also desirable to incorporate in the putties a small amount of awetting agent for which esters of sulfosuccinic acid have proven to bevery useful and also a small amount of trisodium phosphate appears toimprove the consistency of the putties.

Another ingredient which may be added and which is useful in producingthe best results is bentoniteppreferably in a somewhat hydrated orgelatinous form, and this is a further feature of the preferredembodiment of the invention.

While the softening ranges of the putties produced according to thepresent invention will vary, in general they display plasticitythrough-' out a range running from about 37-40" F. up to 113 F., or evensomewhat higher. This should be contrasted with putties prepared withoutthe amides which show excessive hardness and friability at temperaturesaround 37 F. and are too soft to be coherent in the printing operationabove 100 F.

While the proportions of carbohydrate gum, such as dextrin, amide andother constituents, are not critical, nevertheless there are certainranges within which they must be kept in order to give putties which aresatisfactory in their softening range and printing characteristics. Thusthe putties may contain carbohydrate gum, such as dextrin, in amountsfrom 45 to 60% of the total weight. The amide may be used in amountsfrom 6 to 25% and the water content in general should be kept Within therange of to The optimum results will vary somewhat with the particularmembers chosen. For example, when a relatively large amount of urea isused with the dextrin somewhat less water should be employed in order toprevent formation of putties which have too low a softening point.

It is an advantage of the present invention that the putties have a longsoftening range which permits printing operations at elevatedtemperatures. The use of elevated temperatures in many cases presentsadvantages as the printing is accelerated and penetration of the fiberis improved. The long softening ranges of the putties of the presentinvention permit operating at moderately elevated temperatures andrealizing the advantages which result from such operation.

The reference to cellulosic material in the present invention is notintended to be limited to natural cellulose fibers themselves. On thecontrary, it includes not only natural cellulose fibers such as cotton,linen, and the like, but also regenerated cellulose such as viscose andother regenerated cellulosic rayons, and the like.

While the largest field of practical usefulness of the putties of thepresent invention lles in" 4 the printing of ordinary cellulosic fiberssuch as cotton, regenerated cellulose and the like, it is an advantagethat the putties are also useful in printing leather, which has hithertoraised a considerable problem with ordinary printing procedures.

Another field or usefulness of the present invention lies in theprinting of so-called high wetr of the solid product strength papers,that is to say, papers which have urea formaldehyde, and particularlymelamine formaldehyde resins, incorporated in or on the paper, asdescribed in the article by Maxwell, Paper Trade Journal, vol. 116, No.19,pages 39 to42. Prints of excellent strength and sharpness areobtainable in spite of the fact that this type of paper presents seriousdifiiculties to ordinary printing processes, and in fact evenplanographic putties containing vat dyes, described in patent of Kienle,Amick and Kerns, No. 2,364,359, issued December 5, 1944, can only beused to give pastel shades on wet strength paper. The putties of thepresent invention give sharp prints on this type of paper withoutbleeding and in any color strength desired.

The invention will be described in conjunction with the followingspecific examples, but it is not limited to the details therein setforth. The parts are by weight.

Example -1 120 parts of Calcomine Fast scarlet 4BSY (C. I. 326) werepasted with parts of ethyl ether of ethylene glycol and 600 parts ofwater. To this were added 480 parts of urea whereupon the color appearedto go into solution. This color solution was then cold pasted with 1000parts of yellow dextrin in a dough mixer until uniform. The steam valvewas slightly open, the dextrin cooked at a temperature above 165 F. for15 minutes. 200 parts olive oil soap, 40 parts glyceryl mono stearate,10 parts trisodium phosphate and 10 parts of isobutyl ester of sodiumsulfosuccinic acid were added after having been previously pasted with100 parts of boiling water in a separate container. Evaporation ofmoisture from the dough mixer was continued under vacuum until a thinsection, chilled by cooling on an ice cold tin, fractured when bent byhand Example 2 750 parts of the product prepared in the precedingexample and 150 parts of a 7% bentonite gel containing 1% sodiumcarbonate were worked in a small dough mixer to which heat was appliedexternally from a Bunsen burner. The water was evaporated until the sametest was obtained as in Example 1. This product gave good smooth printswhen applied planographically to pigmented rayon and cotton. Theaddition of the bentonite'reduced the tackiness as compared to thatobtained in Example 1.

Example 3 parts of Direct Sky Blue FF (C. I. 518) were pasted with 100parts of ethyl ether of ethylene glycol and 600 parts of water. To

(i. e. on the moist material),

of the above composition.

been previously pasted with 100 parts of boiling 7 water in a separatecontainer. Evaporation of moisture from the dough mixer was continuedunder vacuum until a thin section, chilled by cooling on an ice coldtin, fractured when bent by hand or struck a blow with a bluntinstrument. When printed by the planographic method on a piece ofpigmented rayon, this color transferred uniformly giving a bright,smooth blue print.

Example 4 Pieces of the products of Examples 1, 2, and 3 were formedinto a composite printing block in the form of a design in the differentcolors. When printed by planographic methods on pigmented rayon a sharpprint of the design in the different colors was obtained. No tendencytoward runningof the edges of the different colors in the designs wasnoted.

Example 5 The procedure of Example 1 was followed except that the ureawas replaced by thiourea. The colored product obtained gave brightprints and was entirely satisfactory. When thiourea and dextrin wereadded together without the other substituents a resin-like product wasobtained, the elastic properties of which were only slightly inferior tothe corresponding product with urea and clextrin.

Example 6 The procedure of Example 1 was followed but the urea wasreplaced by the same amount .of melamine. tory prints, but did not havequite the elasticity and softening range of the products using urea orthiourea.

Example 7 120 parts of the dye having Color Index No. 666 are pastedwith 100 parts of the ethyl ether of ethylene glycol and 600 parts ofhot water, after which 480 parts of urea are added.

trade name 4-H, was then added to a small Werner-Pi'leiderer steamheated laboratory vacuum dough mixer, the. above color solution addedand stirred until uniform. It was then heated to 150 F.

150 parts of an olive oil soap powder, parts of glyceryl monostearate,10 parts of sodium diisobutyl sulfosuccinate, 10 parts of trisodiumphosphate, and 100 parts of boiling water are pasted and then added tothe color-dextrin composition in the mixer. The mix is then dried underfive inches of vacuum at -85 C. until a cold thin piece fractures whenbent or struck a sharp blowwith a hammer.

A piece of moist titanium-dioxide pigmented viscose-rayon is used tomake planographic prints After drying, the printed pieces are lightlywrapped in a white 80 x 80 cotton percale and steamed for 10 and 45minutes respectively in an open steamer, and

The product obtained gave satisfac- 1,000 parts of corn dextrin, sold byStein-Hall under the other pieces are steamed for 45 minutes in acottage or pressure steamer at five pounds pressure.

All these prints showed exceptional fastness 'for are added..Planographic prints obtained from thiscolor composition had even bettercolor values than those obtained from the composition prepared inExample 7.

Example 9 1,000 parts of the product sold by Stein-Hall as-S-S Dextrineare pastedin-a Werner-Pfleiderer mixer with 250 parts of water. Whenuniform, the dextrin paste is heated by admitting steam into the steamjacket. The heating and stirring are continued until the paste hashydrated. .40 parts of glyceryl monostearate, 160 parts'ofiLux soap soldby Lever Brothers, .10 parts .of sodium di-isobutyl sulfosuccinate and10 parts of trisodium phosphate are pasted with parts of water.This-composition is then added to the hot dextrin paste and stirring andheating continued. parts of the dye having Color Index No. 382 are thenpasted with 120 parts of the ethyl ether of ethylene glycol and 120parts of water, after'which the color mixture is added to the otheringredients in the mixer. Finally, 120 parts of urea crystals are added,after which, heating, mixing and evaporation of moisture is continueduntil a cooled thin section fractures when struck a blow with a hammer.

When this composition :is printed on a piece of moist 80 x 80 cottonpercale or titanium 'dioxide pigmented viscose rayon fabric or onabsorbent paper, dried, then steamed for half an hour in an opensteamer,a bright scarlet print of good fastness is obtained.

Example 10 A composition is prepared as in the preceding example exceptthe dye having Color Index No. 561 is used in place of the dye havingColor Index No. 382.

Example 11 A composition is prepared as in Example 9 except the dyehaving Color Index No. 698 is used in place of the dye having ColorIndex No. 382.

Example 12' A composition is prepared as in Example 9 except the dyehaving'Color Index No. 620 is used in place of the dye having ColorIndex No. 382.

Example 13 A composition is prepared as in Example 9 except the dyehaving Color Index No. 1078 is used in place of the dye having ColorIndex No. 382.

Example '14 A moist piece of transparent velvet, having a viscose rayonpile, was printed by the planographic process using this printing colorblock Example Aprinting color block Was prepared using the compositionmade in Examples 1, 3 and 7. This was used to print planographically apiece of titanium dioxide pigmented viscose rayon. After drying andsteaming, the fabric was colored strongly and evenly.

While it is an advantage of the present invention that a large number ofdyes capable of being directly aflixed to cellulose without mordantingcan b used, the dyes do not all behave exactly alike. Some of them givegood color values simply by printing, drying, washing, and again drying.In the case of other dyes which are in the majority the color value andfastness properties are improved by steaming in a continuous steamer orin a pressure steamer at about five pounds pressure. In either case thesteaming is usually continued for from 15 to 60 minutes. Where steamingis referred to in the examples, dyes are used which require steaming tobring out the best strength and f astness.

This application is in part a continuation of my copending application,Serial No. 475,049, filed February 6, 1943, which is in turn acontinuation in part of my earlier application, Serial No. 364,531,filed November' fi, 1940.

I claim: I

1. A putty suitable for planographic printing comprising a color capableof being directly fixed on cellulose without mordanting, a carbohydrategum as the essential bodying ingredient and an amide of an acid includedin the. group consisting of'carb-onic acid, thiocarbonic acid andcyanuric acid, all of the ionizable'hydrogen atoms of the acid beingamidified and the amide having at least one free reactive hydrogen atomand being present in the form of a reaction product with thecarbohydrate gum, the putty being hard at room temperature,thermoplastic, displaying plasticity through a range from about 37 to 40F. to about 113 F., and showing good keeping qualities when exposed toordinary moist atmosphere, the putty containing from 45 to 65% ofcarbohydrate gum, and from 6 to of the amide.

2. A putty suitable for planographic printing comprising a color capableof being directly fixed on cellulose without mordanting, a corn dextrinas the essential bodying ingredient and an amide of an acid included inthe group consisting of carbonic, thiocarbonic acid and cyanuric acid,all of the ionizable hydrogen atoms of the acid being amidified and theamide having at least one free reactive hydrogen atom and being presentin the form of a reaction product with the dextrin, the putty being hardat room temperature, thermoplastic, displaying plasticity-through arange from about '37 to 40 F. to about 113 F.,

and showing good keeping qualities when exposed to ordinary moistatmosphere, the putty 8 containing from 45 to 65% of dextrin and from 6to 25% of the amide.

3. A putty suitable for planographic printing comprising a color capableof being directly fixed on cellulose without mordanting, a carbohydrategum as the essential bodying ingredient and urea, the urea being presentas a reaction product with the carbohydrate gum, the putty being hard atroom temperature, thermoplastic, displaying plasticity through a rangefrom about 37 to 40 F. to about 113 F., and showing good keepingqualities when exposed to ordinary moist atmosphere, the puttycontaining from 45 to 65%v of carbohydrate gum, and from 6 to 25% ofurea.

4. A putty suitable for planographic printing comprising a color capableof being directly fixed on cellulose without mordanting, a corn dextrinas the essential bodying ingredient and urea, the urea being present asa reaction product with the dextrin, the putty being hard at roomtemperature, thermoplastic, displaying plasticity through a range fromabout 37 to 40 F. to about 113 F., and showing good keeping qualitieswhen exposed to ordinary moist atmosphere, the putty containing from 45'to 65% of dextrin, and from 6 to 25% of urea.

5. A puttysuitable for planographic printing comprising a color capableof being directly fixed on cellulose without mordanting, a carbohydrategum as the essential bodying ingredient and thiourea, the thiourea beingpresent in the form of a reaction product with the carbohydrate gum, theputty being hard at room temperature, thermoplastic, displayingplasticity through a range from about 37 to 40 F. to about 113 F., andshowing good keeping qualities when exposed to ordinary moistatmosphere, the putty containing from 45 to 65% of carbohydrate gum, andfrom 6 to 25% of thiourea,

6. A putty suitable for planographic printing comprising a color capableof being directly fixed on cellulose without mordanting, a corn dextrinas the essential bodying ingredient and thiourea, the thiourea beingpresent in the form of a reaction product with the dextrin, the puttybeing hard at room temperature, thermoplastic, displaying plasticitythrough a range from about 37 to 40 F. to about 113 F., and showing goodkeeping qualities when exposed to ordinary moist atmosphere, the puttycontaining from 45 to 65% of dextrin and from 6 to 25% of thiourea.

'7. A putty according to claim 1 which contains in addition a waxymaterial. V

8. A putty according to claim 2 which contains in addition a waxymaterial.

9. A putty according to claim 1 which contains in addition a polyhydricalcohol monoester of va higher fatty acid.

10. A putty according to claim z which contains in addition a polyhydricalcohol monoester of a higher fatty acid.

11. A putty according to claim 3 which contains in addition a,polyhydric alcohol monoester of a higher fatty acid.

12. A putty according to claim 4 which contains in addition a polyhydricalcohol monoester of a higher fatty acid.

13. A putty according to claim 5 which contains in addition a polyhydricalcohol monoester of a higher fatty acid.

higher fatty acid.

15, A putty according to claim 3which contains 9 10 in addition a soapand a polyhydric alcohol mono- 18. A putty according to claim 3 which.contains ester of a higher fatty acid. in addition bentonite.

16. A putty according to claim 4 which contains 19. A putty according toclaim 1 which contains in addition a soap and a, polyhydric alcoholmonoa wetting agent. ester of a higher fatty acid, 20. A putty accordingto claim 3 which con 1'7. A putty according to claim 1 which contains awetting agent.

tains in addition bentonite. CHESTER A. AMICK.

